Azo dyestuffs



Patented Dec, 15, 1931 P AIE PATENT TION OF DELAWARE 1 AZO DYESTUF'FSIH. e

No Drawing. Application filed Augie 1, 1928, Serial no. zea ssa a-na in Germany august, 8, 1927.

The'present invention relates to azo dyestuffs, more particularly to azo-dyes corre' sponding to the followinggeneral formula:

wherein aryl stands for anjaryl' group free from anysolubilizing group, such as the SO OH or the COOH group. I

Only a few aromatic amines" are known which, when being used as diazo components and coupled with an arylamide of the 2-hydroxynaphthalene-3-carboxylicv acid, yield azo dyestuffs which are not only of excellent fastness to kier-boiling but also of great fast- 21? ness to light. i

We have now foundithat the 11-amino-3.4- dimethylbenzene halogenated in 6 position yields dyestuffs which fully answer the above mentioned requirements as they are of good 25 fastness to kier boilin and of eminent f astness to light. According to a statement con-f tained in Journal fiir Praktische'Ghemie 46, II, 34 Claus has already prepared 6-chlor-lamino-3.4-dimenthylbenzenebytransforming 6 chlor -8.4- dim'ethylphenyl methylketoxim' into the corresponding acetylc'hlorxylide and saponifying this acetyl compound. However the said compound can be obtainedin'an V easier Way by chlorinating the acetyl compound or the salts of 1-arnino-3.4-dimethylbenzene, or by "substituting chlorine for the amino group in the 1-amino -3 .4-'di1nethyl- 6- nitrobenzene and reducing th'e nitrjo group. The diazo compound of the said base,w hen coupled with the 5-chlor-2-1nethoxy-1-anilide' or the Q-methoxy-l-anilide or the 2.5-dimethoxy-l-anilide of 2-hydroXynaphthalene-3- carboxylic acid, yields. azo dyestuffsdyeing bright neutrally red tobluish red tints of 5 extremely good fastness to kier-boiling and \to light.

The following examples serve to illustrate our invention but are notintende'd'to limit it v thereto; theparts being parts by weight un- 0 less otherwise stated. j

Y (l ;.The cotton fiber is impregnatedin usual manner with the following; grounding liquor: v 4.5 parts of. 2.3-hydroXynaphthoic with 9 parts by volume of'Turkey-red oil of strength,'9. parts of caustic, soda soluv q acid-5 -chlor-2-methoXy-l-anilide-are mixed Eor developing the color, the following diazo Q solution is used; 1.56 partsiofl-ami11052.4-

dimethyl -S-chlorobenzene arediazotized with 2.6 parts by volume of hydrochloric acid of 22 B. and 0.72 parts of sodium nitrite dissolvedinwater, whileicooling with ice.

l/Vhen the diazotation is complete, themass is neutra li'zed with 2 parts of sodium acetate,

therevarethen added'20 parts of. sodium chloride and the whole is made up to one liter. Thusthere' is prod'ucedon the mate- "a:

after it" has beenwa'shed and soaped at the boilpabright bluish-red dyeing of excel lent fastness to kier-bo iling and an eminent fastness to light.

The dyestufi' used inthis sam le has 550b ablyithe following constitution:

CH1: I i

' I (2) The cottonfiber isltreated inthe usu al manner with the following grounding liquor: 4.5 parts of"2.31hydroxynaphthoic acid-4-methoxy-1 -anilide are'mixed with 9 parts byvolume of Turkey-red oil of 50 per 1 cent strength, 9 parts by volume of caustic soda 'solution of 34 B. and 4.5 parts of for- ,maldehyde. of 30% strength and the whole is made up' with water to 1000partsby volume.

Thedevelo'ping operation is] carried out with the diazo solution indicated 'i'nExample 1'.' Thus there is produced on the material, after it has been washed 'and-soaped at the boil,

properties as to fastnes's:

a bright bluish-red-dyeing of verygood 1,. Example 1.; Thus there is produced on'the one liter.

The dyestuff used in this example has probably the following constitution:

CH3 I 7 1 oo-NH-oom 1 on V (3) The cotton'fiberis treated in the usual uor: 4.5'parts of the 4- chlor-2-methoxy-1- i so ' cated in Example 1.

% strength,

anilide of 2.3-hydroxynaphthoic acid; are

mixed with 9 parts by volume of Turkey-red 'oil of 5.0% strength t) partsby volume ofcaustiosoda solution of 34 B. and 4.5 parts ;L

by volume of formaldehyde of whole is made up to one liter. The-develop ingop'eration'iscarried out with the'diazo solu-tion'obtained inthe manner indicated in material; after it has been washedand soap'ed at-the boil, abright bluis'l red dyeing of tic'soda solution of 34 B. and 4.5"parfts of formaldehyde and the whole is made up to The color'is developed withthediazo solution obtained in the manner indiduced on the material, after ithas been washed and, soaped at the boil a bright bluish-red dyeing of good properties asto fastness. I r

The dyestufi used in this example hasprobably the following constitution:

1' s a OOr-NH- V e oom (5) The cotton fiber ispadded in the usual manner with the following grounding liquor: 6' parts of- 2.3-hydroxynaphthoic acid- 2-methoxy-1-anili de are mixed with 12 parts by volume of Turkey-red oil of 50 strength, 12 parts of caustic soda solution of 34 B., 6 partsv by volume of formaldehyde of 80% and the whole is made up toone liter. The

manner with the followinggrounding. liq-V; J

30% and the Thus there. is prodevelopment of the color is carried out by means of the diazo solution in the manner indicated in Example 1. Thus there is produced on the material, after it has been I 1 ,Washed and soaped at the boil, a bright scarlet-red dyeing boiling. w v

The dyestulf used in this example has probably the following formula e CH3 t of very good fastness to kier manner .with the following grounding liquor 3.5 parts of 2.3-hydroxynaphthoic acid-2- naphthalide are mixed with 5'partsby volume of Turkey-red oil lof 50%,strength, 7.5 parts by volume of ca'usti'c soda solution 34 B. and 2. 5-parts of formaldehyde and the whole is made up toone liter. The color is developed with the diazo solution obtained in the manner indicated inExample 1. Thus i The treated intheusual there is produced onthe material, after it has been washed and soaped at the boilia bright reddyeing of good properties as to fastness.

The dyestuff used in this example has prob: ably the following constitution r i V CH3 The cottonfiber is-paddedin the usual manner with the following grounding liquor:

4.5 parts of QB-hydrOXynaphthoicIacid lfl naphthalideare mixed with 9 parts by vol- I ume of, sodium, Turkey-red'loil ofv 50% strength; 11.25" parts by volume of caustic soda solution rof 34. Be; and 4.5 parts of: formaldehyde and the whole is made up to one liter. jTheYcolor" is developed with the diaZo' solution obtainedin the manner indicatedinExamplell Thus there is produced on the material, after it has been washed and soaped at theboil abluish-red dyeing of good fastnessto light. f I T p The dyestuif used in this-example hasprobably the following constitution: I t

OH: 7 CH3 I (8) v The cottonifiber is treated in the usual manner with the following grounding liol uor: 4.5 parts of 2.3-hydroxynaphthoic acid 1,836,118 p a j 3 5-chlor-2'-methyl-1-anilide are mixed with 9 parts by volume of sodium Turkey red oil of 50% strength, 9 parts by volume of caustic soda solution of 34 B. and 4.5 parts by volume of formaldehyde and the whole is made up to one liter. The color is developed with the diazo solution obtained in the manner indicated in Example 1. Thus there is produced on the material, after it has been soaped at the boil, a bright red dyeing of good fastness to kier boiling and to light.

The dyestuif used in this example has probably the following constitution:

CH3 H I N=N C H COMO a Since an object of the present invention is to provide dyestuffs of good fastness properties, it is to be understood that the aromatic nuclei of the general formulae appearwherein aryl stands for a benzene or naphthalene residue which dyestuffs give on cot- OH O-N-aryl a ton bright bluish-red dyeings of very good properties as to fastness.

2. As new products, the azo dyestuffs of the following formula:

wherein X stands for hydrogen, chlorine or the OCH group and Y represents hydrogen, methyl or the OCH group, which dyestufis give on cotton a bright bluish red dyeing of good fastness to kier boiling. I

V 3'1;AsdlWFmdiictssi the? azo .djiestufls35o. the following general formula: .mi

grouper hydrogen, which dyestuffs give on 1 cotfonjabrightbluish-red dyeing of excellent fastnessto kier boiling and particularlygood fastness to light. 4. As new products, the azo dyestuffs of the following formula: p

wherein one X stands for chlorine or the OCH, group and the other X for hydrogen;

which dyestuffs give on cotton a bright bluish-red dyeing of very good properties as to fastness.

5. As new products, the azo dyestufisfof the following formula:

wherein one X stands for chlorine and the other X for hydrogen which dyestufis give 7 on cotton a bright bluish-red dyeing of good 7 properties as to fastness. Y

6. As a new product, the azo dyestuflf of the formula: v i r CH: CH; I

N=N OCH;

i 1 7 As a flew; pre duct;v the azodyestufi of the formula: t 1 I to v. 10 which dyestuff gives on cotton a bright bluish-red dyeingpf goodproperties as to fast:

' In testimony; whk'ef e'o f, We fajifiiz; 011-1} s'igr'latureS.

THOMA; 

